1,3,3-trimethyl-7-oxabicyclo(4.1.0)heptane-2,5-dione

ABSTRACT

SYNTHESIS OF THE NEW COMPOSITION OF MATTER, 1,3,3TRIMETHYL-7-OXABICYCLO(4,1,0)HEPTANE-2,5-DIONE.

United States. Patent 3,775,437 1,3,3-TRI1VlE'II-IYL-7-0XABICYCLO[4.1.0] HEPTANE-2,5-DIONE Donald L. Roberts and Bonita P. Hege, Winston-Salem, N.C., assignors to R. J. Reynolds Tobacco Company,

Winston-Salem, NC. No Drawing. Filed Jan. 4, 1972, Ser. No. 215,427 Int. Cl. C07d 1/06, 1/00 U.S. Cl. 260--348 C 1 Claim ABSTRACT OF THE DISCLOSURE Synthesis of the new composition of matter, 1,3,3- trimethyl-7-oxabicyclo [4.1.0] heptane-2,5-dione.

The present invention relates to a new composition of matter and the synthesis thereof.

The new composition of matter of the present invention is designated chemically as 1,3,3 trimethyl 7- oxabicyclo[4.1.0]heptane 2,5 dione and has the following structural formula:

CH3 ca of Marx and Sondheimer described in Tetrahedron Suppl.

8, Part I, pp. 1-7 (1966). Epoxidation of the 4-'ketoisophorone yields the new compound of this invention. This synthesis is carried out as follows:

A solution of 28 grams of 4-ketoisophorone, 57.6 milliliters of 30% hydrogen peroxide, and 150 milliliters 3,775,437 Patented Nov. 27, 1973 "Ice of methanol was cooled to 15 C. Sodium hydroxide (6 N, 16.6 milliliters) was added dropwise with stirring keeping the temperature of the reaction below 20 C. Stirring was continued for 3.5 hours and then the solution was poured into 300 milliliters of water and extracted with ether. The ether solution was washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give 30 grams of an oil which was characterized as 1,3,3-trimethyl 7 oxabicyclo[4.l.0] heptane -2,5-dione.

Infrared spectrum: 5.85, 6.82, 6.92, 7.19, 7.33, 7.75, 8.05, 8.59, 9.00, 9.30, 9.48, 10.08, 10.50, 10.88, 11.40, 11.65, 12.20, 12.67, and 13.12;.

Nuclear magnetic resonance spectrum: 7' 8.92 (3), 8.70 (3), 8.45 (3), 6.48 (1), 7.74 (1, doublet, J=16.6 cps.), and 6.93 (1, doublet, 11:16.6 cps.).

Analysis calculated for C H- O 168. Found: M/e 168 (mass spectrum).

The compound of the present invention can be converted to the tobacco additive 2-hydroxy 3,5,5 trimethyl 2 cyclohexen 1 1,4 dione by acid or base hydrolysis. For example, 30 grams of the above-described epoxide was placed in 250 milliliters of 20% sulfuric acid containing milliliters of ethanol. This mixture was heated at reflux temperatures for 24 hours and was then cooled. The product was extracted with chloroform to give 25 grams of oil which, on cooling, yielded 7.5 grams of crystalline 2-hydroxy 3,5,5 trimethyl 2 cyclohexen- 1,4-dione, melting point 134-136 C.

Those modifications and equivalents which fall within the spirit of the invention are to be considered a part thereof.

What is claimed is:

1. 1,3,3-trimethyl 7 oxabicyclo[4.1.0]heptane-2,5- dione.

References Cited D. H. Williams et al., Jour. Org. Chem., vol. 33 (3), pp. 998-1002 (1968).

NORMA S. MILESTONE, Primary Examiner U.S. Cl. X.R. 26 8 R UNETED STATES PATENT OFFICE @IEHFICATE @F (IQRECTEN patent 3,775,437 Dated November 27, 1973 Inventor(s) Donald L. Roberts and Bonita P. Hege It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 21, "cyclohexen l 1,4-dione" should read cycloheXen-l,4dione Signed and sealed this 9th day of April 197% (SEAL) Attest:

EDWARD BLFLETCHERJR. 0., MARSHALL DANN Attesting Officer Commissioner of Patents 

